EP1414914B1 - Anorganische partikel und herstellungsverfahren - Google Patents
Anorganische partikel und herstellungsverfahren Download PDFInfo
- Publication number
- EP1414914B1 EP1414914B1 EP02756799A EP02756799A EP1414914B1 EP 1414914 B1 EP1414914 B1 EP 1414914B1 EP 02756799 A EP02756799 A EP 02756799A EP 02756799 A EP02756799 A EP 02756799A EP 1414914 B1 EP1414914 B1 EP 1414914B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- particles
- acid
- surfactant
- pigment
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000010954 inorganic particle Substances 0.000 title description 14
- 239000000049 pigment Substances 0.000 claims abstract description 81
- 239000000203 mixture Substances 0.000 claims abstract description 55
- 239000003973 paint Substances 0.000 claims abstract description 9
- 229920003023 plastic Polymers 0.000 claims abstract description 6
- 239000004033 plastic Substances 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 120
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 119
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 77
- 239000002002 slurry Substances 0.000 claims description 50
- 239000004094 surface-active agent Substances 0.000 claims description 46
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 33
- 239000004408 titanium dioxide Substances 0.000 claims description 31
- 229920002125 Sokalan® Polymers 0.000 claims description 21
- 239000004584 polyacrylic acid Substances 0.000 claims description 20
- 229920001519 homopolymer Polymers 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 150000007529 inorganic bases Chemical class 0.000 claims description 11
- -1 phosphate compound Chemical class 0.000 claims description 10
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 8
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 4
- 235000019830 sodium polyphosphate Nutrition 0.000 claims description 4
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 4
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 3
- 235000007686 potassium Nutrition 0.000 claims 3
- 239000011734 sodium Substances 0.000 claims 3
- 229910052708 sodium Inorganic materials 0.000 claims 3
- 229940126062 Compound A Drugs 0.000 claims 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims 1
- 229910003480 inorganic solid Inorganic materials 0.000 abstract description 17
- 239000000123 paper Substances 0.000 abstract description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 26
- 125000006850 spacer group Chemical group 0.000 description 26
- 239000002585 base Substances 0.000 description 21
- 229910002092 carbon dioxide Inorganic materials 0.000 description 21
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- 235000011941 Tilia x europaea Nutrition 0.000 description 19
- 239000004571 lime Substances 0.000 description 19
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 17
- 238000000149 argon plasma sintering Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 238000001556 precipitation Methods 0.000 description 13
- 229940037003 alum Drugs 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 8
- 239000011575 calcium Substances 0.000 description 8
- 229910052791 calcium Inorganic materials 0.000 description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 8
- 239000000920 calcium hydroxide Substances 0.000 description 8
- 235000011116 calcium hydroxide Nutrition 0.000 description 8
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 238000003917 TEM image Methods 0.000 description 7
- 238000013019 agitation Methods 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 239000008399 tap water Substances 0.000 description 6
- 235000020679 tap water Nutrition 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910000323 aluminium silicate Inorganic materials 0.000 description 5
- 239000004927 clay Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 159000000007 calcium salts Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 239000005297 pyrex Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000010952 in-situ formation Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052604 silicate mineral Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- IDCBOTIENDVCBQ-UHFFFAOYSA-N TEPP Chemical compound CCOP(=O)(OCC)OP(=O)(OCC)OCC IDCBOTIENDVCBQ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 238000013031 physical testing Methods 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/021—Calcium carbonates
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/021—Calcium carbonates
- C09C1/022—Treatment with inorganic compounds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3653—Treatment with inorganic compounds
- C09C1/3661—Coating
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/68—Particle size between 100-1000 nm
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
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- C01P2004/32—Spheres
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- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/38—Particle morphology extending in three dimensions cube-like
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- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/675—Oxides, hydroxides or carbonates
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/385—Oxides, hydroxides or carbonates
Definitions
- Inorganic particles have a wide variety of uses as pigments or as additives to pigments that are important in the manufacture of paints, plastics, paper, laminates, coatings and other applications.
- inorganic pigments with desired characteristics (i.e., particle size, shape, coating and/or crystallinity) for the particular application.
- the prior art mixes, blends, or coats inorganic base particles with other inorganic solids to obtain compositions with useful properties such as brightness, opacity, and light scattering.
- insufficient mechanical dispersion of the base particle and other inorganic solids cause the composition to flocculate or agglomerate reducing, among other things, light-scattering, brightness and opacity.
- the tendency to flocculate or agglomerate can also be reduced by coating the inorganic base particles with suitable inorganic solids that effect the surface charge and other properties.
- Titanium dioxide base particles are often incorporated into paint, plastic, paper, or other coating systems. This pigment imparts desirable properties such as, for example, brightness, opacity, light scattering and durability.
- the crowding effect becomes even more serious when pigment particles are blended or mixed in a formulation, which often causes agglomeration of the particles in the resultant composition. This effect is particularly seen in some papermaking processes.
- an extender also called a spacer or filler
- Some spacers and fillers include calcium carbonate, clay, silica, alumina, and other metal oxide particles.
- spacers and fillers have a lower cost than the base inorganic solid (i.e., titanium dioxide) and therefore reduce the cost of the resultant pigment composition.
- PCC spacer particles are deposited on the surface of titanium dioxide base particles by bubbling carbon dioxide through a slurry containing lime and titanium dioxide. This precipitation method achieves the making of PCC spacers, but does not provide proper control over the precipitated particle size.
- Common problems include insufficient size of the precipitated spacers and agglomeration of the spacers. These problems are due in part to the complexity of many factors that influence the formation of the spacers, such as reactant concentrations, additives, temperature, processing pH, aging periods.
- US 5.551.975 discloses pigments comprising structured aggregate clays which are reaction products of kaolin clays and colloidal silicas and spacer particles such as titanium dioxide.
- EP 0 803 550 discloses spherical SiO 2 particles with a size of from 5 to 500 nm coated at individual points with TiO 2 Fe 2 O 3 or ZrO 2 particles with a size of less than 60 nm, wherein the coated SiO 2 particles can be aftercoated with silanes or further metal oxides.
- EP 0 799 865 discloses fine particles composed of a core and a surface layer, said core being composed of a nucleus formed from (a) titanium dioxide or (b) iron oxide or (c) a mixture of iron oxide and titanium dioxide and an outer layer of titanium dioxide.
- the present invention provides methods and compositions for changing the characteristics of pigments by precipitating inorganic solids in the presence of a suitable surfactant.
- the present invention provides compositions and methods that are cost-effective and produce inorganic compositions with weak or minimal agglomeration and improved light-scattering efficiency, brightness and/or opacity. It has also been found that inorganic particles precipitated on the base particle can have substantially spherical shape with an aspect ratio of from about 0.7 to about 1.5 and be a particular size that improves the light-scattering efficiency, brightness and/or opacity of the pigment composition.
- the present invention provides a pigment composition
- a pigment composition comprising one or more inorganic base particles and one or more substantially spherical shaped calcium carbonate spacer particles having an aspect ratio of between about 0.7 and about 1.5 deposited thereon and a surfactant selected from the group consisting of polyacrylic acid homopolymers, polyacrylic acid copolymers, and mixtures thereof, and a water soluble phosphate compound; the inorganic base particles having a particle size of between about 0.1 (10 -7 metres) and about 0.5 microns (5 ⁇ 10 -7 metres) and calcium carbonate spacer particles having a particle size range between about 0.1 (10 -7 metres) and about 1 micron (10 -6 metres).
- the present invention provides a pigment composition according to claims 2 to 4.
- a pigment composition is provided as per claims 5 and 6.
- the present invention provides a pigment composition as per claims 7 to 8.
- another embodiment of the present invention provides a method of preparing the pigment composition of the invention as per claims 10 to 13.
- the present invention provides paints, plastics or paper as per claim 14.
- inorganic solids can be one or more than one inorganic particles. Inorganic solids also can be a spacer or surface coatings. Examples of inorganic solids include, but are not limited to particles of the following inorganic materials including those in hydrous form: oxides of silicon, titanium, zirconium, zinc, magnesium, aluminum, yttrium, antimony, cerium, and tin; sulfates of barium and calcium; sulfides of zinc; carbonates of zinc, calcium, magnesium, lead and mixed metals, such as naturally occurring dolomite which is a carbonate of calcium and magnesium, nitrides of aluminum; phosphates of aluminum, calcium, magnesium, zinc, and cerium; titanates of magnesium, calcium, and aluminum; fluorides of magnesium and calcium; silicates of zinc, zirconium, calcium, barium, magnesium, mixed alkaline earths and naturally occurring silicate minerals and the like; aluminosi
- Preferred inorganic particles are silica, titanium dioxide, zirconium oxide, zinc oxide, magnesium oxide, tin oxide, calcium carbonate, magnesium carbonate, calcium phosphate, aluminosilicates including alkali and alkaline earth aluminosilicates and naturally occurring aluminosilicate and the like, calcium silicates and naturally occurring silicate minerals and the above mixtures or composites thereof.
- Most preferred inorganic particles include titanium dioxide, calcium carbonate, clay, silica, zirconia, CeO 2 and the like. These inorganic particles can be used in the present compositions in a wide variety of weight-percentages easily determined by those skilled in the art.
- These inorganic particles can be deposited on the base pigment as discrete deposits or can be separate particles alone without the base particle, which can be further processed on the base particle.
- these inorganic particles can be deposited on the base pigment by in situ precipitation as discrete deposits.
- Spacer particles include inorganic particles that are not the base particles, which are calcium carbonate, spacer particles. These spacer particles can be deposited on the base particle or can be separate. The spacer particles are substantially spherical in shape.
- Spacer precursors include reactants that form the spacer particle upon a chemical reaction. Spacer precursors are not the spacer particle but must react to form the spacer particle. Preferred spacer precursors include, but are not limited to lime and CO2 gas for precipitation of calcium carbonate.
- the resultant pigment composition comprises one or more inorganic base particle with one or more other inorganic particle deposited on the surface of the base particle.
- preferred compositions of the present invention include one or more carbonate particles deposited thereon and a surfactant, the pigment composition having a particle size range between about 0.1 (10 -7 metres) and about 0.5 microns (5 ⁇ 10 -7 metres).
- Applicants have found that using a surfactant alters the morphology and size of the inorganic precipitated solid. Characteristics include external particle size, shape, coating, crystallinity, or combinations thereof
- the precipitated inorganic solids have a substantially spherical shape for certain embodiments of the present invention.
- substantially spherical shapes include inorganic particle deposits that are of a smooth rounded shape that lack projections and/or cavities on the surface. Examples of substantially spherical shapes that are useful for this invention include, but are not limited to, spherical, spheroidal, globular and the like. These substantially spherical shapes have an aspect ratio of about 1, most preferably between about 0.7 and 1.5. The aspect ratio includes the ratio of length to height of the particle or length divided by the width of the particle. If the particle is round, the length and width have equal dimensions and the aspect ratio is about 1.
- non-spherical shapes have an aspect ratio of greater than 1.5.
- Non-spherical shapes include irregular shaped inorganic particles that have significant projections and/or cavities on the surface. Such shapes include square, cubic, rectangular, needle, rods, flakes, and the like.
- Inorganic solids suitable for precipitation on the base particle include, for example, calcium carbonate, silica, alumina, zirconia or combinations thereof. These non-spherical shapes have a high aspect ratio above 1.5.
- Surfactants are surface active agents that can alter the morphology of the inorganic precipitate.
- Suitable surfactants for use in the present invention include anionic, cationic, amphoteric, and non-ionic surfactants.
- the surfactant may be water soluble or hydrophobic.
- Suitable surfactants must interact with the precipitation of the inorganic solids on one or more base particles. The surfactant aids in viscosity, dispersibility, stability and resistance to flocculation when in a slurry.
- Suitable surfactants include polyacrylic acid homopolymer.
- polyacrylic acid includes polyacrylic acid derivatives.
- Some examples of polyacrylic acids and/or derivatives thereof include polyacrylic acid homopolymers, polyacrylic acid copolymers, and mixtures thereof.
- the acrylic acid homopolymers and acrylic acid copolymers of the present invention include at least one comonomer selected from the group consisting of maleic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, acrylamide, acrylonitrile, ethylene, propylene, styrene and esters of the above acids, wherein the homopolymers or copolymers have been partially or completely neutralized with a neutralizing agent having a monovalent group.
- These surfactants can be present in amounts up to about 5 weight-percent.
- the surfactant is present in amounts of from about 0.05 to about 2 weight-percent, more preferably from about 0.2 to about 1 or 2 weight-percent; and most preferably from about 0.2 to about 0.5 weight-percent based on the total weight of titanium dioxide.
- Suitable phosphate surfactants for use in the present invention include water soluble phosphate compounds, such as for example, tetrapotassium pyrophosphate, sodium polyphosphate, tetrasodium pyrophosphate (Tetron TM ), sodium tripolyphosphate, potassium tripolyphosphate, sodium hexametaphosphate (Calgon TM ), phosphoric acid, and the like.
- water soluble phosphate compounds such as for example, tetrapotassium pyrophosphate, sodium polyphosphate, tetrasodium pyrophosphate (Tetron TM ), sodium tripolyphosphate, potassium tripolyphosphate, sodium hexametaphosphate (Calgon TM ), phosphoric acid, and the like.
- the present invention includes a pigment composition comprising one or more inorganic base particles and one or more substantially spherical shaped calcium carbonate spacer solids deposited thereon, the pigment composition having a particle size range between about 0.1 (10 -7 metres) and about 0.5 microns (5 ⁇ 10 -7 metres).
- the preferred base pigment of the present invention includes titanium dioxide. Titanium dioxide pigment bases are produced commercially in two crystalline polymorphic forms, namely the rutile form, which can be produced by either the chloride and sulfate processes and the anatase form which is normally produced by the sulfate process. Both of these processes are well known in the art.
- the titanium dioxide may include small quantities of impurities (i.e., iron), additives (i.e., potassium oxide), and surface coatings. Surface coatings are distinguishable from discrete particle deposits or precipitated particles. Generally, surface coatings are coatings of one or more layer around the base particle, as opposed to discrete deposits precipitated on the base particle.
- the TiO 2 base pigments useful in the process of this invention will have a substantially uniform particle size.
- the process of the present invention comprises the formation of an initial aqueous slurry of the base pigment.
- Slurries of base pigment can be made by methods known in the art. Titanium dioxide slurries, for example, of the present invention have a TiO 2 solids content of less than about 50%, preferably less than about 40%, and more preferably less than about 30% by weight of the slurry.
- discrete calcium carbonate particles are deposited by precipitation on titanium dioxide base pigment.
- the precipitation reaction is conducted in the presence of a surfactant as defined above.
- the surfactant is present before the precipitation reaction is started.
- the surfactant is used in titanium dioxide pigments, the surfactant is present in amounts of from about 0.05 to about 2 weight-percent, more preferably from about 0.2 to about 1 weight-percent; and most preferably from about 0.2 to about 0.5 from the prior art that uses blending.
- the discrete calcium carbonate particles preferably have diameters of between about 0.1 micrometer (10 -7 metres) and about 1 micrometer (10 -6 metres) and are precipitated onto the surface of well-dispersed TiO 2 aqueous slurry.
- Lime and CO 2 gas can be used as the spacer precursors for making CaCO 3 particles.
- inorganic spacer particles such as calcium carbonate (CaC03) are formed in situ on the Ti02 base particle.
- spacer precursors such as hydrated lime (Ca(OH)2) is added. Hydrated lime is thoroughly dispersed in the Ti02 slurry.
- Carbon dioxide gas (CO2) is then bubbled into the mixed slurry converting the hydrated lime (Ca(OH)2) to calcium carbonate (CaC03). It is also passible to use hydrated lime (Ca(OH)2) in dry powder form.
- lime (CaO) can be hydrated separately by mixing with water, i.e., slaking, and this hydrated lime slurry can then be added to the Ti02 slurry having the surfactant.
- the lime (CaO) can be directly added to the TiO2 slurry having the surfactant so that it hydrates in the presence of the TiO2 particles, and this technique is preferred over the above slaking technique.
- the resulting slurry preferably comprises greater than 20 weight percent of precipitated calcium carbonate based on TiO 2 pigment weight.
- the preferred weight percentage of calcium carbonate is between about 20% to about 80% based on the weight of TiO 2 . Addition rate of lime into the TiO 2 slurry will affect the scattering efficiency of the final products.
- the addition rate is controlled according to conductivity or pH of the slurry.
- the conductivity of the slurry can in turn be controlled by the CO 2 purging rate.
- CO 2 gas used in this invention can be pure or blended with air with a fixed ratio (for example, 15/85).
- the CO 2 gas flow rate is very important to not only the pH of the whole system but also the resulting precipitated calcium carbonate properties.
- alum is added to the precipitation reaction to control processing viscosity.
- the weight percentage of alum is between about 0.05 to about 2 % based on the total weight of the pigment.
- Suitable conditions include temperature and pH of the slurry and the precipitation reaction. Preferred pH ranges are from about 6.5 to about 7.5.
- the pH of the slurry is adjusted simultaneously in order to deposit the inorganic solid on the surface of the base titanium dioxide pigment.
- the specific pH can be determined by those skilled in the art and adjusted to a desired pH range used by methods known in the art. For example, if adjustment of the pH of the slurry becomes necessary, such adjustments can be made by simply adding a suitable acid or suitable base as discussed above.
- the temperature of the slurry can be controlled to maximize the deposition of the inorganic particle on the pigment. Preferably, temperatures between about 5°C to about 60°C are needed for the precipitation reaction.
- System pH is also controlled by CO 2 flow rate, lime addition rate, and alum addition (if used). This depends on the batch size and can easily be determined by those skilled in the art. Although conductivity is a more accurate way of controlling the process, we found pH control is simpler and sufficient for the present invention.
- the resulting precipitated calcium carbonate particles have a particle size between about 0.1 (10 -7 metres) to about 1 micron (10 -6 metres).
- the precipitated calcium carbonate particles have a substantially spherical shape.
- the present invention includes an inorganic composition comprising one or more substantially spherical shaped calcium carbonate particles, the particles having a size range between about 0.1 (10 -7 metres) and about 1 microns (10 -6 metres). These substantially spherical shaped calcium carbonate particles can have the surfactant in the composition. Other times, they may not have the surfactant in the final composition.
- Sources of calcium carbonate include spacer precursors as defined above, such as for example, lime and CO2 gas.
- the pigment particles in some embodiments of the present invention can be washed substantially free of soluble salts adhering to the pigment, dried and then subjected to final comminution using fluid energy or other milling techniques known in the art.
- the washed and dried pigment is micronized in a steam micronizer at intensities known by those skilled in the art to produce the desired particle size distribution.
- the pigments produced by the methods of the present invention are suitable for use in paints, plastics, and coatings, where brightness and opacity and other desirable properties are needed.
- test methods for light scattering efficiency, brightness and opacity in paper and paints are known in the art.
- TAPPI methods such as T-220 - physical testing of pulp handsheets that tests light scattering coefficients and paper strength, T-425 tests opacity of paper, T-452 tests-brightness of pulp, paper, and paperboard.
- ASTM methods such as D 2805 tests hiding power of paints by reflectometry, and D 2745 tests relative tinting strength of white pigments by reflectance measurements.
- TiO 2 slurry TiONA 4000, Millennium Inorganic Chemicals, about 79% solids, sulfate anatase
- TiONA 4000 Millennium Inorganic Chemicals, about 79% solids, sulfate anatase
- the slurry contains 0.25% (based on TiO 2 weight) of calcium salt of polyacrylic acid.
- the slurry is heated to 45°C.
- 6 ml of 10% alum solution was added.
- a gas flow of CO 2 (industrial grade) was introduced into the slurry.
- 136 g of dry reagent grade lime was slowly added into 10% alum solution (with lime & CO 2 ).
- the final pH is about 7.5.
- the total reaction consumes total 24 ml of alum solution and takes about 1 hour and 10 minutes.
- the particle size of the PCC is about 0.1 (10 -7 metres) to about 0.3 micrometers (3 ⁇ 10 -7 metres).
- the finished sample was submitted for TEM examination. The TEM graph is shown in Figure 3 .
- TiO 2 slurry (RCS-P, Millennium Inorganic Chemicals, about 74% solids, chloride rutile) was diluted with 300g of tap water.
- the slurry contains 0.3% of TKPP (tetra-potassium pyrophosphate based on TiO 2 weight), no alum was used.
- a gas flow of CO 2 (industrial grade) was introduced into the slurry.
- 36 g of dry lime was slowly added into the slurry with strong agitation.
- the processing pH was controlled at 7 to 7.5 by adding CO 2 and lime.
- the final pH is about 8.
- the total reaction takes about 1 hour and 10 minutes.
- the particle size of the PCC is about 0.1 (10 -7 metres) to about 0.3 micrometers (3 ⁇ 10 -7 metres).
- TiO 2 slurry (RL11A, Millennium Inorganic Chemicals, about 73% solids, sulfate rutile) was diluted with 300g of tap water and dispersed with 0.5% of calcium salt of polyacrylic acid (based on TiO 2 weight) in 600 ml beaker. The slurry is heated to 45°C. To the slurry, 3 ⁇ 4 g of 10% alum solution was added. A gas flow of CO 2 (industrial grade) was introduced into the slurry. 34 g of dry lime was slowly added into the slurry with strong agitation. The processing pH was controlled at 7 to 7.5 by adding 10% alum solution (with CO 2 & lime). The final pH is about 7. The total reaction consumes total 5 ml of alum solution and takes about 1 hour and 10 minutes. The particle size of the PCC is about 0.1 (10 -7 metres) to about 0.3 micrometers (3 ⁇ 10 -7 metres).
- TiO 2 slurry (AT-1 slurry, Millennium Inorganic Chemicals, about 78% solids, sulfate anatase) was diluted with 100g of tap water and dispersed in a 250 ml polyacrylic acid. The slurry is heated to 45°C. A gas flow of CO 2 /air with 15/85 ratio was introduced into the slurry. 34 g of dry lime was slowly added into the slurry with strong agitation. The processing pH was controlled at 7 by gas flow rate. The final pH is about 7.6. The total reaction takes about 40 minutes. The particle size of the PCC is about 0.1 to about 0.3 micrometers.
- Figures 5 and 6 are Transmission Electron Micrographs of pigment obtained using a recipe described in the prior art in which CaCO 3 with particle sizes between about 20 to about 40 nanometers can be made to distribute on the TiO 2 surface without the in situ use of surfactants. As is clearly shown, the CaCO 3 particles are very small with mixed non-spherical shape in the range of about 20 to about 40 nanometers.
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- Silicon Compounds (AREA)
Claims (14)
- Pigmentzusammensetzung, die ein oder mehrere anorganische Basisteilchen und ein oder mehrere, darauf abgelagerte, im Wesentlichen kugelförmige Calciumcarbonat-Distanzteilchen mit einem Seitenverhältnis von zwischen etwa 0,7 und etwa 1,5 und ein grenzflächenaktives Mittel, das aus der Gruppe von Polyacrylsäurehomopolymeren, Polyacrylsäurecopolymeren und Gemischen derselben und einer wasserlöslichen Phosphatverbindung ausgewählt ist, umfasst; wobei die anorganischen Basisteilchen eine Teilchengröße von zwischen etwa 0,1 und etwa 0,5 µm aufweisen und die Calciumcarbonat-Distanzteilchen einen Teilchengrößenbereich zwischen etwa 0,1 und etwa 1 µm aufweisen.
- Pigmentzusammensetzung nach Anspruch 1, wobei die Basisteilchen Anatas- oder Rutil-Titandioxid sind.
- Pigmentzusammensetzung nach Anspruch 1, wobei das grenzflächenaktive Mittel aus der Gruppe von Polyacrylsäurehomopolymeren, Polyacrylsäurecopolymeren und Gemischen derselben ausgewählt ist.
- Pigmentzusammensetzung nach Anspruch 3, wobei das grenzflächenaktive Mittel ein Homopolymer von Acrylsäure oder ein Copolymer von Acrylsäure umfasst, wobei das Homopolymer von Acrylsäure oder das Copolymer von Acrylsäure mindestens ein Comonomer umfasst, das aus der Gruppe von Maleinsäure, Methacrylsäure, Itaconsäure, Crotonsäure, Fumarsäure, Acrylamid, Acrylnitril, Ethylen, Propylen, Styrol und Estern der Säuren ausgewählt ist, wobei das Homopolymer oder Copolymer teilweise oder vollständig mit einem Neutralisationsmittel mit einer einwertigen Gruppe neutralisiert ist.
- Pigmentzusammensetzung nach Anspruch 1, wobei das grenzflächenaktive Mittel eine wasserlösliche Phosphatverbindung ist.
- Pigmentzusammensetzung nach Anspruch 5, wobei die wasserlösliche Phosphatverbindung aus der Gruppe von Tetrakaliumpyrophosphat, Natriumpolyphosphat, Tetranatriumpyrophosphat, Natriumtripolyphosphat, Kaliumtripolyphosphat, Natriumhexametaphosphat, Phosphorsäure und Gemischen derselben ausgewählt ist.
- Pigmentzusammensetzung nach Anspruch 1, wobei es sich bei dem einen oder den mehreren anorganischen Basisteilchen um Titandioxid handelt und das grenzflächenaktive Mittel aus der Gruppe von Polyacrylsäurehomopolymeren, Polyacrylsäurecopolymeren und Gemischen derselben ausgewählt ist.
- Pigmentzusammensetzung nach Anspruch 1, wobei es sich bei dem einen oder den mehreren anorganischen Basisteilchen um Titandioxid handelt und das grenzflächenaktive Mittel eine wasserlösliche Phosphatverbindung ist.
- Pigmentzusammensetzung nach Anspruch 8, wobei das grenzflächenaktive Mittel eine Phosphatverbindung ist, die aus der Gruppe von Tetrakaliumpyrophosphat, Natriumpolyphosphat, Tetranatriumpyrophosphat, Natriumtripolyphosphat, Kaliumtripolyphosphat, Natriumhexametaphosphat, Phosphorsäure und Gemischen derselben ausgewählt ist.
- Verfahren zur Herstellung der Pigmentzusammensetzung nach einem der Ansprüche 1 bis 9, das die folgenden Stufen umfasst:(a) Herstellen einer wässrigen Aufschlämmung von Basispigmentteilchen;(b) Zugabe des grenzflächenaktiven Mittels und einer Quelle für Calciumcarbonat zu der Aufschlämmung und(c) Ausfällen des Calciumcarbonats auf den Basis-Titandioxid-Pigmentteilchen unter derartigen Bedingungen, dass im Wesentlichen kugelförmiges Calciumcarbonat mit einem Seitenverhältnis von zwischen etwa 0,7 und etwa 1,5 und einem Teilchengrößenbereich zwischen etwa 0,1 und etwa 1 µm auf den Basis-Titandioxid-Pigmentteilchen gebildet wird, wobei die Basispigmentteilchen einen Teilchengrößenbereich zwischen etwa 0,1 und etwa 0,5 µm aufweisen.
- Verfahren nach Anspruch 10, wobei das grenzflächenaktive Mittel aus der Gruppe von Polyacrylsäurehomopolymeren, Polyacrylsäurecopolymeren und Gemischen derselben ausgewählt ist.
- Verfahren nach Anspruch 10, wobei das grenzflächenaktive Mittel ein Polyacrylsäurehomopolymer oder -copolymer umfasst, das mindestens ein Comonomer umfasst, das aus der Gruppe von Maleinsäure, Methacrylsäure, Itaconsäure, Crotonsäure, Fumarsäure, Acrylamid, Acrylnitril, Ethylen, Propylen, Styrol und Estern der Säuren ausgewählt ist, wobei das Homopolymer oder Copolymer teilweise oder vollständig mit einem Neutralisationsmittel mit einer einwertigen Gruppe neutralisiert ist.
- Verfahren nach Anspruch 10, wobei das grenzflächenaktive Mittel eine wasserlösliche Phosphatverbindung ist, die aus der Gruppe von Tetrakaliumpyrophosphat, Natriumpolyphosphat, Tetranatriumpyrophosphat, Natriumtripolyphosphat, Kaliumtripolyphosphat, Natriumhexametaphosphat, Phosphorsäure und Gemischen derselben ausgewählt ist.
- Anstrichmittel, Kunststoff oder Papier, die das Pigment nach einem der Ansprüche 1, 7 oder 8 umfassen.
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US09/921,502 US6743286B2 (en) | 2001-07-30 | 2001-08-01 | Inorganic particles and methods of making |
US921502 | 2001-08-01 | ||
PCT/US2002/024134 WO2003011981A1 (en) | 2001-07-30 | 2002-07-30 | Inorganic particles and methods of making |
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EP (1) | EP1414914B1 (de) |
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DE102006062641A1 (de) * | 2006-12-28 | 2008-07-03 | Ltn Nanovation Ag | Stabile Dispersionen nanoskaliger Partikel |
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-
2001
- 2001-08-01 US US09/921,502 patent/US6743286B2/en not_active Expired - Fee Related
-
2002
- 2002-07-30 BR BR0211617-0A patent/BR0211617A/pt not_active Application Discontinuation
- 2002-07-30 AT AT02756799T patent/ATE452164T1/de not_active IP Right Cessation
- 2002-07-30 WO PCT/US2002/024134 patent/WO2003011981A1/en not_active Application Discontinuation
- 2002-07-30 EP EP02756799A patent/EP1414914B1/de not_active Expired - Lifetime
- 2002-07-30 DE DE60234774T patent/DE60234774D1/de not_active Expired - Fee Related
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2004
- 2004-04-30 US US10/837,060 patent/US20040202601A1/en not_active Abandoned
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US20030024437A1 (en) | 2003-02-06 |
ATE452164T1 (de) | 2010-01-15 |
BR0211617A (pt) | 2004-11-09 |
DE60234774D1 (de) | 2010-01-28 |
US20040202601A1 (en) | 2004-10-14 |
US6743286B2 (en) | 2004-06-01 |
EP1414914A1 (de) | 2004-05-06 |
WO2003011981A1 (en) | 2003-02-13 |
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